JP2944209B2 - Mixed esters and their use as lubricants in plastic molding compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates primarily to oligomeric complex esters used as lubricants to process thermoplastics, especially those based on vinyl polymers.
omplex ester).

Generally, thermoplastic resins are processed at temperatures above the melting point. The type of processing is determined by the properties of the plastic used and the form of the desired end product.
The most widely used processing methods include injection molding, injecting a molten material into a mold, cooling the material to a temperature below its melting point, and removing a molded product, calendering for forming a film or sheet between a pair of calender rolls, Alternatively, there are various extrusion methods for producing, for example, tubes, profiles, pipes, and similar products.

Many plastic melts have strong adhesion to the metal parts of the processing machine, which can often cause problems during processing. In injection molding, for example, it is more difficult to remove a molded product from a mold, and there is a risk of causing damage to the molded product, and production is stopped due to a part that cannot be removed. Sometimes. In film production, the adhesion of the melt causes uncontrollable stretching when the film is pulled from the roll, resulting in roughness and thickness variations.

To overcome these problems, a lubricant and a release agent are added during processing; this forms a release film between the polymer melt and the processing machine.

Having a hydroxyl or acid value of 0 to 6 and a) fatty acid dicarboxylic acid, cycloaliphatic dicarboxylic acid and / or aromatic dicarboxylic acid; b) aliphatic polyol; A lubricant is known for forming a thermoplastic resin composition comprising a mixed ester consisting of an aliphatic monocarboxylic acid having the following carbon atoms:
No. 907,768). Preferred esters are esters based on fatty acids having up to 22 carbon atoms.

At least in applications where high quality is required, two groups of surface lubricants are preferably used for large groups containing vinyl polymers, especially for polyvinyl chloride.

The two groups are the various semi-synthetic waxes based on montan wax and the oligomeric esters prepared from aliphatic dicarboxylic acids, polyols and fatty acids.

The above two types of lubricants are one of the most effective of all lubricants, but they each, when considered individually, represent only a few of the performance requirements of an ideal lubricant. It simply has Montanic acid derivatives exhibit good exfoliation behavior (especially in the case of PVC processing), impart high strength to the melt, and have very good heat resistance to the final product Imparts properties. However, since the lubricant has a disadvantage that it tends to cause fogging (particularly in the case of PVC whose impact resistance is not improved), it has a sufficient peeling behavior. At the expense of, in some cases, their use can be severely limited.

Furthermore, when a conventional montanic acid ester is used to produce a calendered PVC film, the pressure in the roll gap of the processing machine increases, and a high stress (nip pressure) is generated. In contrast, both simple fatty acid esters, such as, for example, stearyl stearate, and the oligomeric fatty acid esters reduce the nip pressure during processing of PVC. However, at the same time, it has a disadvantage that the melt strength and heat resistance of PVC are reduced. In PVC without improved impact resistance, simple fatty acid esters and oligomeric fatty acid esters have better transparency than montanic acid derivatives.

Other lubricants and release agents that are currently available only partially fulfill the required performance, so that mixtures of lubricants are generally used. However,
In that procedure, the formulation becomes very complicated and the possibility of bad interactions between many components arises. Furthermore, the use of more compounding components requires larger storage equipment and more complex metering and mixing equipment during processing.

Therefore, there is a need for a lubricant that combines the positive properties of a montanic acid derivative with the positive properties of an oligomeric fatty acid ester, while at the same time not having the aforementioned disadvantages of the lubricant.

It has now been found that certain mixed esters made from dicarboxylic acids, long-chain monocarboxylic acids and aliphatic polyols satisfy the above-mentioned requirements particularly well.

Thus, the present invention provides a long chain aliphatic monocarboxylic acid having 24 to 40 carbon atoms, an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, and 3 to 10 carbon atoms and 3 to 6 carbon atoms. The present invention relates to a mixed ester of an aliphatic polyol having an OH group. The mixed ester has a KOH of 8-30 mg / g.
Acid number, hydrolysis value of 130-220 mg KOH / g, and 90
It has a melt viscosity of 200 to 2000 mPa · S at ° C.

The mixed esters according to the invention are produced by esterifying a dicarboxylic acid and a long-chain monocarboxylic acid with a polyol.

Dicarboxylic acids have from 2 to 12 carbon atoms in the molecule and can be aliphatic, cycloaliphatic or aromatic. Examples of suitable dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, maleic acid, fumaric acid, There are citraconic acid, mesaconic acid, itaconic acid, cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, camphoric acid, hexahydrophthalic acid, phthalic acid, terephthalic acid and isophthalic acid.
A preferred dicarboxylic acid is adipic acid.

The long-chain monocarboxylic acid has 24 to 40 carbon atoms in the molecule, and is preferably technical grade montanic acid produced by oxidatively bleaching crude montan wax. The montanic acid is a mixture of monocarboxylic acids, the acid C ₂₆ -C ₃₄ in a high proportion have (approximately 80%), 25
It has a low proportion of acids having not more than carbon atoms.

Aliphatic polyols have from 3 to 12 carbon atoms and from 3 to 6 OH groups in the molecule. Examples include glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, xylitol, mannitol and sorbitol. Preferred polyols are glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol.

The mixed esters according to the invention can be prepared by esterification methods known per se. For example, a long-chain aliphatic monocarboxylic acid is esterified using a dihydric or polyhydric polyol. In this case, the resulting partial ester still contains a plurality of free hydroxyl groups, and the mixed ester is then prepared by reacting those hydroxyl groups with a suitable dicarboxylic acid. However, it is also possible to use a dicarboxylic acid to first esterify some of the hydroxyl groups of the polyol and then to react the remaining free hydroxyl groups of the resulting ester with the long chain aliphatic monocarboxylic acid. it can.

The reaction was carried out with the final mixed ester being KO / g.
It is carried out in such a way that it has an acid number of 8 to 30 mg of H, preferably an acid number of 8 to 20 mg of KOH per gram, and a hydrolysis value of 130 to 220 mg of KOH per gram, preferably 130 to 200 mg of KOH per gram.

The mixed ester according to the present invention comprises a dicarboxylic acid, a long-chain monocarboxylic acid and a polyol, (0.4-1.0) :( 1.5
To 2.5): (2.5 to 3.5) equivalent ratio, preferably (0.7 to
0.9): (1.8-2.2): Included in the equivalent ratio of (2.8-3.2).
Mixed esters containing adipic acid, montanic acid and trimethylolpropane in a suitable equivalent ratio of 0.8: 2: 3 are particularly preferred.

The mixed esters according to the invention are solid and have a melt viscosity at 90 ° C. of 200 to 2000 mPa · S, preferably 200 to 800 mPa · S.
It has a melt viscosity of mPa · S.

The mixed ester is used as a lubricant in a thermoplastic resin molding composition. For example, polyvinyl chloride, copolymers of vinyl chloride which can be prepared by known methods (eg suspension polymerization, bulk polymerization or emulsion polymerization), copolymers of vinyl chloride containing up to 30% by weight of comonomers and graft polymers of polyvinyl chloride and polyacrylonitrile Used as a lubricant. Such comonomers include, for example, vinyl acetate, vinylidene chloride, vinyl ethers, acrylonitrile, acrylates, maleic monoesters or maleic diesters or olefins.

Preferred thermoplastic molding compositions are polyvinyl chloride, polyvinylidene chloride, (ethylene-vinyl acetate) copolymers, polyacrylonitrile, copolymers of vinyl chloride and vinyl acetate and graft polymers derived therefrom, or of the thermoplastic resins. Based on the mixture.

The amount added is 0.05 to 5% by weight, based on the polymer. If the molding composition is based on bulk PVC or suspended PVC, the amount added is preferably 0.05-1% by weight, based on the polymer, and if based on emulsified PVC, the amount added is Is preferably from 1.0 to 5% by weight, especially from 2 to 4% by weight, based on

The mixed esters according to the invention are incorporated into the polymer in a conventional manner during the preparation of the molding composition.

In addition to the mixed esters according to the invention, the plastic molding compositions furthermore comprise fillers, heat stabilizers, sunscreens, antistatic agents, flameproofing agents, reinforcing agents, pigments, dyes, processing aids, lubricants, release agents. Molding agents, impact modifiers, antioxidants, blowing agents or optical brighteners can be included in conventional amounts.

The mixed esters according to the invention reduce the nip pressure that occurs during the production of rolled films. Its action is stronger than that of known fatty acid mixed esters. At the same time, it prevents adhesion of the molding composition to the roll, and has better transparency than commercially available montan wax.

 Hereinafter, the present invention will be further described with reference to examples.

Example 1 Montanic acid complex ester 1 402.7 g of montanic acid (acid value = 139.2 mg of KOH / g)
Melted in a wit jar, then with stirring
67.1 g of trimethylolpropane and 1.32 cm ³ of butyltin tris-2-ethylhexanoate as a catalyst were added. The mixture was heated to 125 ° C. under a nitrogen atmosphere while stirring and constantly removing the water formed in the esterification reaction by distillation. The acid value of the mixture is KOH / g
When it fell below 10 mg, 29.2 g of adipic acid were added. The reaction was continued under the same conditions until the acid value was again reduced to less than 10 mg of KOH / g, and then 2.5 cm ^{3 of} 35% hydrogen peroxide.
Was added to improve the color, then the batch was stirred for a further 15 minutes before being dried and filtered.

A hard yellowish wax having an acid number of 8.3 mg KOH / g, a hydrolysis number of 180 mg KOH / g and a melt viscosity of 573 mPa · S (90 ° C.) was obtained.

Example 2 Montanic acid complex ester 2 402.7 g of montanic acid (acid value = 139.2 mg of KOH per 1 g)
To melted as in Example 1, then at 80 ° C., trimethylol propane 67.1 g, 29.2 g adipic acid, hypophosphorous acid 2.1 cm ^3, and methanesulfonic acid 0.37 cm ³ were added.
The mixture was heated to 120 ° C. while stirring and removing the water of reaction by distillation. The acid value of the mixture is 1
NaOH 7.7c at 10% concentration when KOH drops below 10mg / g
m ³ was added to neutralize the acid added as a catalyst. The product was then bleached with 2.5 cm ³ of hydrogen peroxide. As a result, by drying and filtering, KOH10.
5 mg acid number, 172 mg KOH / g hydrolysis number, and 459 mP
A pale yellow wax having a melt viscosity of a · S (90 ° C.) was obtained.

Example 3 Montanic acid complex ester 3 125.0 kg of montanic acid (acid value = 137 mg of KOH / g) was melted and heated to 80 ° C. Next, 20.6 kg of trimethylolpropane and 400 g of p-toluenesulfonic acid were added thereto with stirring. The temperature of the mixture was raised to 130 ° C. while removing the water of reaction by distillation. After about 100 minutes,
The acid number of the batch dropped to less than 10 mg KOH / g. 8.94 Kg of adipic acid were added and the mixture was heated for another 2 hours while stirring and removing the water formed in the esterification reaction by distillation.

To neutralize the catalyst acid, 10% NaOH60
0 cm ³ was added. The product was subsequently bleached by adding 700 cm ³ of 35% strength hydrogen peroxide. Filtration yielded a yellow wax having an acid number of 19.0 mg KOH / g, a hydrolysis number of 187 mg KOH / g, and a melt viscosity of 202 mPa · S (90 ° C.).

In the following examples, the following products were used as comparisons to the prior art: A Oligomeric fatty acid esters: mixed esters of stearic acid, pentaerythritol acid and adipic acid B Glycerol montanate C Ethylene glycol montanate Example 4 Montanic acid complex ester 3 was formulated into the following formulation and tested using a laboratory roll mill (manufactured by Collins) having a roll diameter of 150 mm and a roll surface width of 350 mm.
The amount applied was 200 g. The electrically heated roll was adjusted to a temperature of 195 ° C. Their rotation speed is 15 / 20rpm
Met. The resulting supporting pressure (nip pressure) _PK (in kilonewtons) was measured. The laboratory roll mill also had an automatic reversing device for the dispensed compound. The force required for this reversing operation is a measure of the adhesive force of the compound dispensed on the chrome roll (adhesive force F _K : unit is Newton).

Suspended PVC (K value about 60) 100 parts by weight Thiotine stabilizer 1.5 parts by weight MBS impact modifier 4.0 parts by weight Acrylate-containing processing aid 1.0 parts by weight Epoxidized soybean oil 0.5 parts by weight Glycerol monostearate 0.8 parts by weight Test Product 0.3 parts by weight Experiment Test product I Oligomer montanate 3 II Oligomer fatty acid ester A III Glycerol montanate B IV Ethylene glycol montanate C The adhesion-free time of these mixtures
ime) and final stability were tested on a roll mill at 190 ° C., 15/20 rpm.

Example 5 Formulation Suspended PVC (K value about 60) 100 parts by weight Thiotine stabilizer 1.4 parts by weight MBS impact modifier 5.0 parts by weight Acrylate-containing processing aid 1.0 parts by weight Glycerol monooleate 0.9 parts by weight Test product 0.3 the parts by weight adhesion F _K and the nip pressure P _K, on the to-roll mill for laboratory as in example 4 was measured.

EXPERIMENTAL TEST PRODUCT I Oligomer montanate 3 II Oligomer fatty acid ester A III Glycerol montanate B The following values were measured on a roll mill (190 ° C: 15 / 20r
pm).

Example 6 Montanic acid complex esters 1 and 2 were tested for transparency in the following formulations.

Suspended PVC (K value about 60) 100 parts by weight Acrylate-containing processing aid 1.0 parts by weight Octyltin stabilizer 1.5 parts by weight Glycerol monooleate 0.3 parts by weight Test product 0.6 parts by weight Plates were formed by plasticizing on top and pressing it at 0.5mm and 2.0mm. They were tested in neutral gray light using a clarity measuring device.

Example 7 The peeling behavior of montanic acid complex esters 1 and 3 was tested in the following formulation: 100 parts by weight of bulk PVC (K value about 57) 8 parts by weight of MBS impact modifier 8 parts by weight of acrylate-containing processing aid 1.2 parts by weight 1.6 parts by weight thiotin stabilizer 1.0 part by weight epoxidized soybean oil 0.3 parts by weight glycerol monooleate 0.3 parts by weight Test product 0.6 parts by weight The test was carried out on a roll mill at 190 ° C. and 15/20 rpm. The experiment was stopped when the dispensed compound turned brown.

Examples 4 and 5 show that oligomeric montanic acid ester 3 significantly reduces the nip pressure. Also, according to Examples 4 to 7, oligomer montanic acid esters 1, 2
And 3 also have advantages with respect to release behavior and transparency.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 101/00 C08L 101/00 // (C08K 5/10 5: 103 5:11) (72) Inventor P. Salt, Jan-Peter Federal Republic of Germany Day 8900 Augsburg, Oblatterwalstrasse 44 (58) Fields studied (Int. Cl. ⁶ , DB name) C08K 5/10-5/12 C07C 69/30-69/606 CA (STN ) REGISTRY (STN)

Claims (8)

(57) [Claims] A long chain aliphatic monocarboxylic acid having 24 to 40 carbon atoms, an aliphatic dicarboxylic acid having 2 to 12 carbon atoms, and 3 to 12 carbon atoms and 3 to 6 carbon atoms. A mixed ester of an aliphatic polyol having an OH group, the mixed ester having an acid value of 8 to 30 mg of KOH / g, a hydrolysis value of 130 to 220 mg of KOH / g, and a melt viscosity of 200 to 2000 mPa · S at 90 ° C. . 2. The mixed ester according to claim 1, wherein the long-chain aliphatic monocarboxylic acid is technical grade montanic acid. 3. The mixed ester according to claim 1, wherein the polyol is glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or dipentaerythritol. 4. The mixed ester according to claim 1, which is produced from montanic acid, adipic acid and trimethylolpropane. 5. Use of the mixed esters according to claim 1 as lubricants for processing thermoplastic molding compositions. 6. The mixed ester according to claim 1, wherein
A thermoplastic resin molding composition containing 0.05 to 5%. 7. Polyvinyl chloride, polyvinylidene chloride,
7. The thermoplastic resin molding composition according to claim 6, which is based on (ethylene-vinyl acetate) copolymer, polyacrylonitrile, a graft polymer or copolymer of vinyl chloride and vinyl acetate, or a mixture of said thermoplastic resins. 8. A filler, a heat stabilizer, a light-shielding agent, an antistatic agent,
7. The thermoplastic resin according to claim 6, further comprising a flameproofing agent, a reinforcing agent, a pigment, a dye, a processing aid, a lubricant, a release agent, an impact resistance improving agent, an antioxidant, a foaming agent, or a fluorescent whitening agent. Molding composition.